JP2022551960A - Fuel efficient lubricating composition - Google Patents

Abstract

The present disclosure is generally directed to low viscosity, low volatility lubricating compositions. The lubricating composition of the present disclosure comprises an oil of lubricating viscosity containing a lubricating base oil and a hydrocarbon oil. The hydrocarbon oil constitutes at least 20% by weight of the oil of lubricating viscosity, has a kinematic viscosity at 100° C. of less than 3.7 cSt, and a NOACK volatility (as measured by ASTM D5800) of less than 25% by weight. The lubricating composition further comprises a polyalkenylsuccinimide dispersant and optionally other formulation additives. Lubricating compositions have been shown to increase fuel economy in internal combustion engines.

Description

There is increasing interest in improving the fuel efficiency of internal combustion engines. Automakers have improved fuel economy through improvements that take advantage of advances in engine design, lubricants that provide better oxidation stability, wear protection, and reduced friction.

Lubricant viscosity and base oil viscosity are two of the major drivers of fuel economy through lubricants. Low lubricant viscosity often leads to improved fuel efficiency for internal combustion engines. However, there are practical limits that govern the viscosity range available for lubricant compositions.

Lubricant life is limited by many factors, including exposure to combustion gases, high temperature, and pressure. Additionally, oil consumption, the loss of lubricant from the crankcase during normal operation of the engine, is a major factor affecting low viscosity fluids. Base oil volatility is one of many factors that govern oil consumption, but moving to lower viscosity lubricants to achieve improvements in fuel economy results in significant reductions in oil life. obtain.

SUMMARY OF THE DISCLOSURE The present disclosure relates to lubricants for internal combustion engines that can provide improved fuel economy at least without reducing the useful life of the lubricant and/or impacting engine cleanliness and durability performance. . This can be achieved by using a low viscosity, low volatility base oil in combination with an ashless succinimide dispersant.

The present disclosure includes lubricating base oils and hydrocarbon oils, wherein the hydrocarbon oil is at least 20% by weight of the oil of lubricating viscosity, kinematic viscosity at 100° C. of less than 3.7 cSt, and NOACK volatility of less than 25% by weight. 1.2 to 4 wt. is a 0W-XX multigrade composition and XX is selected from 8, 12, 16, and 20 according to SAE J300.

In another embodiment, the present disclosure comprises a lubricating base oil and a hydrocarbon oil, wherein the hydrocarbon oil is 20-95% by weight of the oil of lubricating viscosity, a kinematic viscosity of less than 3.7 cSt at 100°C, and a low viscosity, low volatility lubricating composition having an oil of lubricating viscosity with a NOACK volatility (as measured by ASTM D5800) of less than 20 wt%; 1.2 to 4 wt% of a polyalkenylsuccinimide dispersant; , the lubricating composition is a 0W-XX multigrade composition and XX is selected from 8, 12, 16, and 20 according to SAE J300.

In another embodiment, the present disclosure comprises a lubricating base oil and a hydrocarbon oil, wherein the hydrocarbon oil is at least 20% by weight of the oil of lubricating viscosity, a kinematic viscosity at 100° C. of less than 3.7 cSt, and 25 A low viscosity, low volatility lubricating composition having an oil of lubricating viscosity with less than wt. % NOACK volatility (as measured by ASTM D5800), 1.2-4 wt. 0.1-3% by weight of an antiwear agent such as zinc dithiophosphate and 0.5-3% by weight selected from one or more of an overbased calcium salicylate detergent and a basic magnesium salicylate detergent. and 0.08 to 1.2 wt% polymer viscosity modifier, the lubricating composition is a 0W-XX multigrade composition according to SAE J300, and XX is 8, selected from 12, 16, and 20;

The present disclosure further relates to a method of lubricating an internal combustion engine, the method comprising supplying the composition described herein to at least one lubrication system within the internal combustion engine.

The present disclosure also provides the methods described herein for improving fuel economy in internal combustion engines without reducing the useful life of the lubricating composition and/or without affecting engine cleanliness and durability performance. of any one of the lubricating compositions of

Various features and embodiments are described below by way of non-limiting illustration. The present disclosure relates to a method for lubricating an internal combustion engine.

The disclosed technology provides low volatility lubricating compositions, methods for lubricating internal combustion engines with low volatility lubricating compositions, and uses as disclosed above. The term "low volatility" when used in reference to a hydrocarbon oil means that the hydrocarbon oil has an evaporative loss of less than 25% by weight as measured by the ASTM D5800 Noack test. The lubricating compositions disclosed herein comprise an oil of lubricating viscosity, including a lubricating base oil and a hydrocarbon oil, wherein the hydrocarbon oil is at least 20% by weight of the oil of lubricating viscosity, according to the ASTM D5800 Noack test. When measured, it has a kinematic viscosity measured at 100° C. of no more than 3.7 cSt and an evaporative loss of less than 25% by weight. The oil of lubricating viscosity may further comprise one or more suitable lubricating base oils different from those of the hydrocarbon oils.

Lubricating base oils (in addition to and distinct from hydrocarbon oils) Lubricating base oils include natural and synthetic oils, oils derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined oils, refined Contains oils, re-refined oils, or mixtures thereof. A more detailed description of unrefined, refined and re-refined oils is provided in paragraphs [0054]-[0056] of WO2008/147704 (a similar disclosure is No., see [0072]-[0073]). A more detailed description of natural and synthetic lubricating oils is described in paragraphs [0058]-[0059] of WO2008/147704, respectively (similar disclosures are provided in US Patent Publication No. 2010/0197536, See [0075]-[0076]). Synthetic oils may also be produced by Fischer-Tropsch reactions and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be prepared by a Fischer-Tropsch gas-liquid synthesis procedure, as well as other gas-liquid oils.

Lubricating base oils are also described in "Appendix E-API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils", April 2008 edition, section 1.3 Sub-heading 1.3. May be defined as specified in the "Base Stock Categories". API guidelines are also summarized in US Pat. No. 7,285,516 (see column 11, line 64 to column 12, line 10). In one embodiment, the lubricating base oil can be an API Group II, Group III, Group IV oil, or mixtures thereof. The five base oil groups are:

The amount of oil of the lubricating base oil present in the lubricating composition is typically the balance remaining after subtracting the sum of the amounts of the hydrocarbon oil and other performance additives of this disclosure from 100 weight percent (wt%). is.

In one embodiment, the lubricating base oil comprises at least 30 wt% Group II or Group III base oil. In another embodiment, the base oil comprises at least 60 wt% Group II or Group III base oil, or at least 80 wt% Group II or Group III base oil. In one embodiment, the lubricant composition comprises less than 20 wt% Group IV (ie, polyalphaolefin) base oil. In another embodiment, the lubricating composition comprises less than 10 wt% Group IV base oil. In one embodiment, the lubricating composition is substantially free (ie, contains less than 0.5 wt%) of Group IV base oils.

Ester-based fluids, characterized as Group V oils, possess a high level of solvency as a result of their polar nature. Adding low levels (typically less than 10% by weight) of esters to a lubricating composition can significantly increase the solvency power of the base oil. Esters can be broadly classified into two categories, synthetic and natural. Ester-based fluids have kinematic viscosities at 100° C. suitable for use in engine oil lubricants, such as 2 cSt to 30 cSt, or 3 cSt to 20 cSt, or even 4 cSt to 12 cSt. In one embodiment, the lubricating composition comprises at least 2% by weight ester-based fluid. In one embodiment, the lubricating composition comprises at least 4% by weight ester-based fluid, or at least 7% by weight ester-based fluid, or even at least 10% by weight ester-based fluid.

Hydrocarbon Oil The hydrocarbon oil of the present invention comprises one or more saturated hydrocarbons containing at least one hydrocarbyl branch sufficient to provide fluidity at both very low and high temperatures. The hydrocarbons of the present invention may include natural and synthetic oils, oils derived from hydrocracking, hydrotreating, and hydrofinishing, refined oils, bio-derived oils, re-refined oils, or mixtures thereof.

Synthetic hydrocarbon oils may be produced by the isomerization of primarily linear hydrocarbons to produce branched hydrocarbons. Linear hydrocarbons may be naturally occurring, synthetically prepared, or derived from Fischer-Tropsch reactions or similar processes. The hydrocarbon oils may be derived from hydroisomerized waxes, typically hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be prepared by Fischer-Tropsch gas-to-liquid synthesis procedures, as well as other gas-to-liquid oils.

Suitable hydrocarbon oils may also be obtained from natural renewable sources. Natural (or biobased) oils refer to materials derived from renewable biological sources, organisms, or entities, as distinguished from materials derived from petroleum or equivalent raw materials. Natural sources of hydrocarbon oils include fatty acid triglycerides, hydrolyzed or partially hydrolyzed triglycerides, or transesterified triglyceride esters such as fatty acid methyl esters (or FAMEs). Suitable triglycerides include, but are not limited to, palm oil, soybean oil, sunflower oil, rapeseed oil, olive oil, linseed oil, and related materials. Other sources of triglycerides include, but are not limited to algae, animal tallow, and zooplankton. Linear and branched hydrocarbons can be refined or extracted from vegetable oils and can be hydrorefined and/or hydroisomerized to produce hydrocarbons in a manner similar to synthetic oils. In some embodiments, at least 50% by weight of the hydrocarbon oil is bio-derived. In other embodiments, at least 55%, or at least 60%, or at least 65%, or at least 70%, or at least 80%, or at least 90% by weight of the hydrocarbon oil is of biological origin. . In one embodiment, the hydrocarbon oil is bio-derived and substantially free, ie, does not contain less than 0.5% by weight of ester functional groups, based on the weight of the hydrocarbon oil.

Hydrocarbons are generally understood to consist essentially of carbon and hydrogen atoms, although they may often contain minor amounts of heteroatoms. The hydrocarbon oils of the present invention are free or substantially free of heteroatoms, except for impurities and contaminants that may be introduced from processing or manufacturing.

The hydrocarbon oils of the present invention comprise hydrocarbon compounds containing from 16 carbon atoms up to 60 carbon atoms and at least one hydrocarbon branch containing at least 1 carbon atom. In one embodiment, the hydrocarbon compound contains at least 18 or at least 22 carbon atoms, with the proviso that the longest continuous chain of carbon atoms is 24 carbons or less in length. In one embodiment, hydrocarbon oils include hydrocarbon compounds containing from 22 to 38 carbon atoms, with the proviso that the longest continuous chain of carbon atoms is 24 carbons or less in length. In one embodiment, the hydrocarbon oil is bio-derived and comprises hydrocarbon compounds having no more than 24 carbon atoms and a continuous chain of at least 30 total carbon atoms.

Alternatively, hydrocarbon oils may be described as paraffinic or isoparaffinic compounds.

Mineral oils often contain cyclic structures, ie cycloparaffins, also called aromatics or naphthenes. In one embodiment, the hydrocarbon oil comprises saturated hydrocarbon compounds that are free or substantially free of cyclic structures. In one embodiment, the hydrocarbon oil is substantially aliphatic (95% or more by weight) and contains less than 5% by weight of cyclic hydrocarbons.

In one embodiment, the hydrocarbon oil has a kinematic viscosity of at least 0.7 cSt, or at least about 0.9 cSt, or at least about 1.1 cSt, measured at 100°C. In one embodiment, the hydrocarbon oil is less than 3.7 cSt at 100°C, or less than 3.6 cSt at 100°C, or less than 3.5 cSt at 100°C, or less than 3.4 cSt at 100°C, or less than 3.2 cSt at 100 ^° C has a kinematic viscosity of less than In further embodiments, the hydrocarbon oil has a closed cup flash point of at least 50°C, or at least 60°C, or at least 75°C, or at least 100°C.

In one embodiment, the hydrocarbon oil has an evaporative loss (also called Noack volatility) of less than 25 wt% wt% as measured by ASTM D5800. In one embodiment, the evaporative loss is less than 20 wt%, or less than 18 wt%, or less than 15 wt%. In one embodiment, the hydrocarbon oil has a kinematic viscosity of less than 3.7 cSt at 100°C and an evaporation loss of less than 25 wt%.

The lubricating composition comprises an oil of lubricating viscosity comprising at least 20% by weight of hydrocarbon oil, based on the weight of the oil of lubricating viscosity. In one embodiment, the oil of lubricating viscosity is at least 30 wt% hydrocarbon oil, or at least 35 wt%, or at least 40 wt%, or at least 50 wt%, or at least 60 wt%, or at least 70 wt% It may contain hydrocarbon oils. In another embodiment, the oil of lubricating viscosity is 90% by weight hydrocarbon oil, based on the weight of the oil of lubricating viscosity. In one embodiment, the oil of lubricating viscosity is 100% by weight hydrocarbon oil, based on the weight of the oil of lubricating viscosity.

In some embodiments, the oil of lubricating viscosity may comprise at least 20% by weight of hydrocarbon oil, based on the weight of the oil of lubricating viscosity. In another embodiment, the oil of lubricating viscosity may comprise 20% to 95% by weight hydrocarbon oil, or 25% to 75% by weight, or 30% to 60% by weight hydrocarbon oil.

An oil of lubricating viscosity containing a lubricating base oil and a hydrocarbon oil can have a viscosity index of greater than 100. In some embodiments, the viscosity index is greater than 115, or greater than 125. In other embodiments, the viscosity index is 110-130, or 115-125, or 117-122.

式中、各Ｒ^１は、独立してアルキル基であり、多くの場合、ポリイソブチレン前駆体に基づいて、５００～５０００の分子量（Ｍ_ｎ）を有するポリイソブチレン基であり、Ｒ^２は、アルキレン基、一般的にエチレン（Ｃ_２Ｈ_４）基である。 Polyalkenylsuccinimide Dispersant The lubricating compositions of the present disclosure further comprise a polyalkenylsuccinimide dispersant. Dispersants are generally well known in the lubricant art and include primarily what are known as ashless dispersants and polymeric dispersants. Ashless dispersants are so called because they do not contain metals as supplied and therefore do not normally contribute to sulfated ash when added to lubricating oils. However, they can interact with surrounding metals when added to lubricants containing metal-containing species. Ashless dispersants are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long chain alkenyl succinimides and have a wide variety of chemical structures, including those represented by Formula (I).

wherein each R ¹ is independently an alkyl group, often a polyisobutylene group having a molecular weight (M _n ) of 500 to 5000, based on the polyisobutylene precursor, and R ² is an alkylene group, typically an ethylene (C ₂ H ₄ ) group.

Such molecules are generally derived from the reaction of alkenyl acylating agents with polyamines, and include a variety of amides and quaternary ammonium salts, as well as the simple imide structures shown above, as well as a wide variety of isomers between the two moieties. Can be combined. In formula (I) above, the amine moiety is shown as an alkylenepolyamine, but other aliphatic and aromatic monoamines and polyamines may also be used. Also, a variety of attachment modes of the R ¹ group to the imide structure are possible, including various cyclic linkages. The ratio of carbonyl groups of the acylating agent to nitrogen atoms of the amine is from 1:0.5 to 1:3, in other cases from 1:1 to 1:2.75 or from 1:1.5 to 1:2. can be 5; Succinimide dispersants are described in further detail in US Pat. Nos. 4,234,435 and 3,172,892 and EP0355895.

In certain embodiments, the dispersant is a small amount of chlorine or Prepared by processes involving the presence of other halogens. Such dispersants typically have several carbocyclic structures at the attachment of the hydrocarbyl substituent to the acidic or amide "head" group. In other embodiments, the dispersant is prepared by a thermal process involving an "ene" reaction without the use of any chlorine or other halogens, as described in U.S. Pat. No. 7,615,521, Dispersants made in this manner are often derived from high vinylidene (i.e., greater than 50% terminal vinylidene) polyisobutylene (see column 4, line 61 through column 5, line 30 and Preparation B. see). Such dispersants typically do not contain the above carbocyclic structures at the point of attachment. In certain embodiments, the dispersant is prepared by free radical catalyzed polymerization of high vinylidene polyisobutylene with an ethylenically unsaturated acylating agent, as described in US Pat. No. 8,067,347.

Dispersants for use in the present lubricating compositions may be derived from high vinylidene polyisobutylene having greater than 50, 70, or 75% terminal vinylidene groups (alpha and beta isomers) as the polyolefin. In certain embodiments, succinimide dispersants can be prepared by a direct alkylation route. In other embodiments, the succinimide dispersant can include a mixture of direct alkylation and chlorine routed dispersants.

Dispersants suitable for use in the present lubricating compositions include succinimide dispersants. In one embodiment, the dispersant may be present as a single dispersant. In one embodiment, the dispersant may be present as a mixture of two or three different dispersants, at least one of which may be a succinimide dispersant.

Succinimide dispersants can be derived from aliphatic polyamines or mixtures thereof. Aliphatic polyamines can be aliphatic polyamines such as ethylene polyamines, propylene polyamines, butylene polyamines, or mixtures thereof. In one embodiment, the aliphatic polyamine may be ethylene polyamine. In one embodiment, the aliphatic polyamine may be selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine stills, and mixtures thereof.

Succinimide dispersants can be derived from aromatic amines, aromatic polyamines, or mixtures thereof. Aromatic amines include 4-aminodiphenylamine (ADPA) (also known as N-phenylphenylenediamine), derivatives of ADPA (described in US Patent Publication Nos. 2011/0306528 and 2010/0298185), nitro Aniline, aminocarbazole, amino-indazolinone, aminopyrimidine, 4-(4-nitrophenylazo)aniline, or combinations thereof. In one embodiment, the dispersant is a derivative of an aromatic amine, the aromatic amine having at least three discontinuous aromatic rings.

The succinimide dispersant may be a derivative of a polyetheramine or polyetherpolyamine. A typical polyetheramine compound will contain at least one ether unit and be chain terminated with at least one amine moiety. Polyether polyamines can be based on polymers derived from C ₂ -C ₆ epoxides such as ethylene oxide, propylene oxide, and butylene oxide. Examples of polyether polyamines are sold under the Jeffamine® brand and are commercially available from Huntman Corporation located in Houston, Texas.

Dispersants can also be post-treated by conventional methods by reaction with any of a variety of agents. Among these are boron compounds, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydrides, nitriles, epoxides, and phosphorus compounds. In one embodiment, a succinimide dispersant can be post-treated with boron to yield a borated dispersant. In one embodiment, the succinimide dispersant comprises at least one boron-containing dispersant and at least one boron-free dispersant. In one embodiment, the lubricating composition is free or substantially free of boron-containing succinimide dispersants.

The polyalkenylsuccinimide dispersant is from 1.2% to 4% by weight of the lubricating composition, or from 1.5% to 3.8% by weight of the composition, or from 1.2% to 3% by weight of the composition. , or in an amount from 2.0% to 3.5% by weight. When a mixture of two or more dispersants comprises a succinimide dispersant, each of those dispersants may comprise from 0.01% by weight of the lubricant composition to 4 wt%, or 0.1 wt% to 3.5 wt%, or 0.5 wt% to 3.5 wt%, or 1.0 wt% to 3.0 wt%, or 0.5 wt% to It is understood that 2.2% by weight may be present independently in the composition. In one embodiment, the polyalkenylsuccinimide dispersant is polyisobutylene succinimide. In another embodiment, the polyalkenylsuccinimide dispersant is polyisobutylene succinimide and is present in the lubricating composition in an amount of 1.2-4% by weight.

In one embodiment, the polyalkenylsuccinimide dispersant is a boron-containing succinimide dispersant in an amount of 1.2-4% by weight of the lubricating composition. In another embodiment, the polyalkenylsuccinimide dispersant is a mixture of a boron-free succinimide dispersant and a boron-containing succinimide dispersant. When both the boron-containing dispersant and the boron-free dispersant are present, the ratio of the one or more boron-containing dispersants to the one or more boron-free dispersants is 4:1 to 1 on a weight basis. :4, or 3:1 to 1:3, or 2:1 to 1:3, or 1:1 to 1:4 by weight. In another embodiment, the one or more boron-containing dispersants are present in an amount of from 0.8% up to 2.1% by weight, and the one or more boron-free dispersants are present in the lubricating composition. It is present in amounts from 0.8% up to 4% by weight.

Other Performance Additives The compositions of the present invention may optionally contain one or more additional performance enhancing additives. These additional performance-enhancing additives include one or more of metal deactivators, viscosity modifiers, detergents, friction modifiers, antiwear agents, corrosion inhibitors, dispersants (different from those of the present invention), agents, dispersant viscosity modifiers, extreme pressure agents, antioxidants, antifoam agents, demulsifiers, pour point depressants, seal swell agents, and any combination or mixture thereof. Typically, a fully formulated lubricating oil will contain one or more of these performance-enhancing additives, and often contains multiple performance-enhancing additive packages.

In one embodiment, the present invention provides antiwear agents, dispersant viscosity modifiers, friction modifiers, viscosity modifiers, antioxidants, overbased detergents, dispersants (different from those of the present invention), or Lubricating compositions are provided that further include these combinations, where each of the listed additives may be a mixture of two or more of that type of additive. In one embodiment, the present invention provides antiwear agents, dispersant viscosity modifiers, friction modifiers, viscosity modifiers (typically olefin copolymers such as ethylene-propylene copolymers), antioxidants (phenolic and amine a lubricating composition further comprising an overbased detergent (including overbased sulfonates and phenates), or a combination thereof, wherein each of the listed additives comprises It may be a mixture of two or more of the additives.

Another additive is an antiwear agent. Examples of antiwear agents include phosphorus containing antiwear/extreme pressure agents such as metal thiophosphates, phosphate esters and their salts, phosphorus containing carboxylic acids, esters, ethers and amides, and phosphates. be done. In certain embodiments, the phosphorus antiwear agent is from 0.01 to 0.2, or from 0.015 to 0.15, or from 0.02 to 0.1, or from 0.025 to 0.08, or from 0.025 to 0.08. It may be present in an amount that delivers 01-0.05 percent phosphorus. Often the antiwear agent is a zinc dialkyldithiophosphate (ZDDP or ZDP).

Zinc dialkyldithiophosphates can be designated as primary zinc dialkyldithiophosphates or secondary zinc dialkyldithiophosphates, depending on the structure of the alcohol used in their preparation. In some embodiments, the compositions of the present invention comprise a primary zinc dialkyldithiophosphate. In some embodiments, the compositions of the present invention comprise secondary zinc dialkyldithiophosphates. In some embodiments, the composition of the present invention comprises a mixture of primary and secondary zinc dialkyldithiophosphates. In some embodiments, component (b) is a mixture of a primary zinc dialkyldithiophosphate and a secondary zinc dialkyldithiophosphate, wherein the ratio (by weight) of the primary zinc dialkyldithiophosphate to the secondary zinc dialkyldithiophosphate is is at least 1:1, or at least 1:1.2, or at least 1:1.5 or 1:2, or 1:10. In some embodiments, component (b) is a mixture of primary and secondary zinc dialkyldithiophosphates that are at least 50 weight percent primary, or even at least 60, 70, 80, or 90 weight percent primary. In some embodiments, component (b) does not include a primary zinc dialkyldithiophosphate.

The phosphorus antiwear agent may be present at 0 wt% to 3 wt%, or 0.1 wt% to 1.5 wt%, or 0.5 wt% to 0.9 wt% of the lubricating composition.

In one embodiment, the present invention provides a lubricating composition further comprising an ashless antioxidant. Ashless antioxidants may include one or more of arylamines, diarylamines, alkylated arylamines, alkylated diarylamines, phenols, hindered phenols, sulfurized olefins, or mixtures thereof. In one embodiment, the lubricating composition comprises an antioxidant, or mixtures thereof. antioxidants, from 0% to 15%, or from 0.1% to 10%, or from 0.5% to 5%, or from 0.5% to 3%, by weight of the lubricating composition; or may be present from 0.3% to 1.5% by weight.

The diarylamine or alkylated diarylamine can be phenyl-α-naphthylamine (PANA), alkylated diphenylamine, or alkylated phenylnaphthylamine, or mixtures thereof. Alkylated diphenylamines can include dinonylated diphenylamine, nonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine, didecylated diphenylamine, decyldiphenylamine, and mixtures thereof. In one embodiment, the diphenylamine may include nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine, or mixtures thereof. In one embodiment, alkylated diphenylamines may include nonyldiphenylamine or dinonyldiphenylamine. Alkylated diarylamines can include octyl, dioctyl, nonyl, dinonyl, decyl, or didecylphenylnaphthylamine.

The diarylamine antioxidants of the present invention are 0.1% to 10%, 0.35% to 5%, 0.4% to 1.2%, or even 0.5% by weight of the lubricating composition. % to 2%.

Phenolic antioxidants may be simple alkylphenols, hindered phenols, or bound phenolic compounds.

Hindered phenol antioxidants often contain secondary and/or tertiary butyl groups as sterically hindering groups. The phenolic group may be further substituted with a hydrocarbyl group (usually a straight or branched chain alkyl) and/or a bridging group that joins the second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol , 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, 4-dodecyl-2,6-di-tert-butylphenol, or butyl 3-(3, 5-di-tert-butyl-4-hydroxylphenyl)propanoate. In one embodiment, the hindered phenol antioxidant may be an ester and may include, for example, BASF's Irganox™ L-135. In one embodiment, the phenolic antioxidant comprises hindered phenols. In another embodiment, the hindered phenol is derived from 2,6-di-tertbutylphenol.

In one embodiment, the lubricating composition of the present invention comprises 0.01% to 5%, or 0.1% to 4%, or 0.2% to 3%, or Contains phenolic antioxidants in the range of 0.5% to 2% by weight.

Sulfurized olefins are well-known commercial materials and are readily available substantially nitrogen-free, ie, containing no nitrogen functional groups. The olefinic compounds that can be sulfurized are diverse in nature. It contains at least one olefinic double bond, defined as a non-aromatic double bond, ie, one connecting two aliphatic carbon atoms. These materials generally have sulfide bonds containing 1 to 10, such as 1 to 4, or 1 or 2 sulfur atoms.

Ashless antioxidants can be used separately or in combination. In one embodiment of the invention, at least 0.1 weight percent of each of the at least two antioxidants is present, and the total amount of ashless antioxidants is between 0.5 and 5 weight percent. Two or more different antioxidants are used in combination. In one embodiment, at least 0.25-3% by weight of each ashless antioxidant may be present.

In one embodiment, the invention provides a lubricating composition further comprising a molybdenum compound. The molybdenum compound may be selected from the group consisting of molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, amine salts of molybdenum compounds, and mixtures thereof. The molybdenum compound may provide 0 to 1000 ppm, or 5 to 1000 ppm, or 10 to 750 ppm, or 5 ppm to 300 ppm, or 20 ppm to 250 ppm, or 350 ppm to 900 ppm molybdenum to the lubricating composition.

In one embodiment, the lubricating composition of the present invention further comprises a dispersant viscosity modifier. Dispersant viscosity modifiers may be present at 0% to 5%, or 0% to 4%, or 0.05% to 2%, by weight of the lubricating composition.

Suitable dispersant viscosity modifiers include functionalized polyolefins such as ethylene-propylene copolymers functionalized with acylating agents such as maleic anhydride and amines, polymethacrylates functionalized with amines, or Esterified styrene-maleic anhydride copolymers may be mentioned. A more detailed description of dispersant viscosity modifiers can be found in WO 2006/015130 or US Pat. No. 6,117,825. In one embodiment, the dispersant viscosity modifier is U.S. Pat. No. 4,863,623 (see col. 2, see paragraph [0008], and preparation examples are described in paragraphs [0065]-[0073]).

In one embodiment, the present invention provides a lubricating composition further comprising a metal-containing detergent. Metal-containing detergents can be overbased detergents. Overbased detergents, also called overbased salts, or overbased salts, contain excess metal content that would be required for neutralization according to the stoichiometry of the metal and the particular acidic organic compound reacting with the metal. characterized by Overbased detergents may be selected from the group consisting of sulfur-free phenates, sulfur-containing phenates, sulfonates, salixarates, salicylates, and mixtures thereof.

Overbased metal-containing detergents can be sodium, calcium, magnesium salts of phenates, sulfur-containing phenates, sulfonates, salixates and salicylates, or mixtures thereof. Overbased phenates and salicylates typically have a total base number of 180-450 TBN. Overbased sulfonates typically have a total base number of 250-600, or 300-500. Overbased detergents are known in the art. In one embodiment, the sulfonate detergent is at least It can be a predominantly linear alkyl benzene sulfonate detergent with a metal ratio of 8. Linear alkylbenzene sulfonate detergents can be particularly useful to help improve fuel economy. Linear alkyl groups can be attached to the benzene ring anywhere along the linear chain of the alkyl group, but are often attached at the 2, 3 or 4 positions of the linear chain, sometimes primarily at the 2-position. to provide linear alkylbenzene sulfonate detergents. Overbased detergents are known in the art. Overbased detergents range from 0% to 15%, or 0.1% to 10%, or 0.2% to 8%, or 0.5% to 3%, or 0.2% It may be present from wt % to 3 wt %. For example, in heavy duty diesel engines, the detergent may be present at 2% to 3% by weight of the lubricating composition. For passenger car engine applications, the detergent may be present at 0.2% to 1% by weight of the lubricating composition.

Metal-containing detergents contribute sulfated ash to the lubricating composition. Sulfated ash may be determined by ASTM D874. In one embodiment, the lubricating composition of the present invention comprises an amount of metal-containing detergent to deliver at least 0.4% by weight sulfated ash throughout the composition. In another embodiment, the metal-containing detergent provides at least 0.6 wt% sulfated ash, or at least 0.75 wt% sulfated ash, or even at least 0.9 wt% sulfated ash to the lubricating composition. It is present in the amount to be delivered.

The lubricating composition may contain polymeric viscosity modifiers or mixtures thereof. Polymeric viscosity modifiers can be olefin (co)polymers, poly(meth)acrylates (PMA), or mixtures thereof. In one embodiment, the polymeric viscosity modifier is an olefin (co)polymer.

Olefin polymers may be derived from isobutylene or isoprene. In one embodiment, the olefin polymer is prepared from ethylene and higher olefins within the range of C3-C10 alpha-monoolefins, for example the olefin polymer can be prepared from ethylene and propylene.

In one embodiment, the olefin polymer comprises 15-80 mole percent ethylene, such as 30-70 mole percent ethylene, 20-85 mole percent C3-C10 monoolefins, such as propylene, such as 30-70 mole percent It can be a polymer of propylene or greater mono-olefins. Terpolymer versions of olefin copolymers may also be used, which may contain up to 15 mole percent non-conjugated dienes or non-conjugated trienes. A non-conjugated diene or triene can have from 5 to about 14 carbon atoms. Non-conjugated diene monomers or non-conjugated triene monomers can be characterized by the presence of vinyl groups in their structure and can include cyclic and bicyclic compounds. Representative dienes include 1,4-hexadiene, 1,4-cyclohexadiene, dicyclopentadiene, 5-ethyldiene-2-norbornene, 5-methylene-2-norbornene, 1,5-heptadiene, and 1,6 - octadiene.

In one embodiment, the olefin copolymer can be a copolymer of ethylene, propylene, and butylene. Polymers may be prepared by polymerizing a mixture of monomers including ethylene, propylene, and butylene. These polymers are sometimes referred to as copolymers or terpolymers. The terpolymer has from about 5 mol % to about 20 mol %, or from about 5 mol % to about 10 mol % of structural units derived from ethylene, from about 60 mol % to about 90 mol %, or from about 60 mol % to about 75 mol % of structural units derived from propylene, about 5 mol % % to about 30 mol % or from about 15 mol % to about 30 mol % of butylene-derived structural units. Butylene may include any isomers or mixtures thereof, such as n-butylene, isobutylene, or mixtures thereof. Butylene can include butene-1. Commercially available butylenes can include butene-1, as well as butene-2, and butadiene. Butylene may comprise a mixture of butene-1 and isobutylene, wherein the weight ratio of butene-1 to isobutylene is about 1:0.1 or less. The butylenes may include butene-1 and be free or essentially free of isobutylene.

In one embodiment, the olefin copolymer may be a copolymer of ethylene and butylene. The polymer may be prepared by polymerizing a mixture of monomers including ethylene and butylene, wherein the monomer composition is free or substantially free (i.e., less than 1% by weight intentionally added (containing monomers that have been combined). The copolymer may contain 30 to 50 mol percent of structural units derived from butylene and may contain from about 50 mol percent to 70 mol percent of structural units derived from ethylene. Butylene may comprise a mixture of butene-1 and isobutylene, wherein the weight ratio of butene-1 to isobutylene is about 1:0.1 or less. The butylenes may include butene-1 and be free or essentially free of isobutylene.

Useful olefin polymers, especially ethylene-α-olefin copolymers, have number average molecular weights ranging from 4500 to 500,000, such as from 5000 to 100,000, or from 7500 to 60,000, or from 8000 to 45,000. .

In one embodiment, the lubricating composition may include a poly(meth)acrylate polymer viscosity modifier. As used herein, the term "(meth)acrylate" and its cognates mean either methacrylate or acrylate, as is readily understood.

In one embodiment, the poly(meth)acrylate polymer is prepared from a monomer mixture containing (meth)acrylate monomers having alkyl groups of varying lengths. The (meth)acrylate monomers may contain linear or branched alkyl groups. Alkyl groups may contain from 1 to 24 carbon atoms, for example from 1 to 20 carbon atoms.

The poly(meth)acrylate polymers described herein are monomers derived from saturated alcohols such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2- Methylpentyl (meth)acrylate, 2-propylheptyl (meth)acrylate, 2-butyloctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, isooctyl (meth)acrylate , isononyl (meth)acrylate, 2-tert-butylheptyl (meth)acrylate, 3-isopropylheptyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, tridecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, 2- methylhexadecyl (meth)acrylate, heptadecyl (meth)acrylate, 5-isopropylheptadecyl (meth)acrylate, 4-tert-butyloctadecyl (meth)acrylate, 5-ethyloctadecyl (meth)acrylate, 3-isopropyloctadecyl-( meth)acrylates such as meth)acrylates, octadecyl (meth)acrylates, nonadecyl (meth)acrylates, eicosyl (meth)acrylates, oleyl (meth)acrylates derived from unsaturated alcohols, and 3-vinyl-2-butylcyclohexyl (meth)acrylates or cycloalkyl (meth)acrylates such as bornyl (meth)acrylates, and the like.

Other examples of monomers include alkyl (meth)acrylates with long-chain alcohol-derived groups, such as the reaction of (meth)acrylic acid with long-chain fatty alcohols (direct ester (by transesterification) or by reaction of methyl (meth)acrylate with long-chain fatty alcohols (by transesterification), which generally involves the formation of esters such as (meth)acrylates with alcohols of various chain lengths. A mixture of groups is obtained. These fatty alcohols include Oxo Alcohol® 7911, Oxo Alcohol® 7900 and Oxo Alcohol® 1100 from Monsanto; Alphanol® 79 from ICI; Nafol® 1620, Alfol® 610 and Alfol® 810; Epal® 610 and Epal® 810 from Ethyl Corporation; Linevol® 79, Linevol® from Shell AG; Lial® 125 from Condea Augusta, Milan; Dehydad® and Lorol® from Henkel KGaA (now Cognis); ® 7-11 and Acropol ® 91.

In one embodiment, the poly(meth)acrylate polymer comprises a dispersant monomer. Dispersant monomers include monomers that can be copolymerized with (meth)acrylate monomers to contain one or more heteroatoms in addition to the (meth)acrylate carbonyl group. The dispersant monomer may contain nitrogen-containing groups, oxygen-containing groups, or mixtures thereof.

The nitrogen-containing compound may be a (meth)acrylamide or nitrogen-containing (meth)acrylate monomer. Examples of suitable nitrogen-containing compounds include N,N-dimethylacrylamide, N-vinylcarbonamides such as N-vinylformamide, vinylpyridine, N-vinylacetamide, N-vinylpropionamide, N-vinylhydroxyacetamide, N - vinylimidazole, N-vinylpyrrolidinone, N-vinylcaprolactam, dimethylaminoethyl acrylate (DMAEA), dimethylaminoethyl methacrylate (DMAEMA), dimethylaminobutylacrylamide, dimethylaminopropyl methacrylate (DMAPMA), dimethylaminopropylacrylamide, dimethylamino Propylmethacrylamide, dimethylaminoethylacrylamide or mixtures thereof.

Dispersant monomers may be present in amounts up to 5 mol percent of the monomer composition of the (meth)acrylate polymer. In one embodiment, the poly(meth)acrylate is present in an amount of 0-5 mol percent, 0.5-4 mol percent, or 0.8-3 mol percent of the polymer composition. In one embodiment, the poly(meth)acrylate is free or substantially free of dispersant monomers.

In one embodiment, poly(meth)acrylates include block copolymers or tapered block copolymers. Block copolymers are formed from a monomer mixture comprising one or more (meth)acrylate monomers, e.g., a first (meth)acrylate monomer forms a second Form discrete blocks of polymer that bond to discrete blocks. Block copolymers have substantially discrete blocks formed from the monomers in the monomer mixture, whereas tapered block copolymers are composed of a relatively pure first monomer at one end and a relatively pure first monomer at the other end. It may be composed of a second monomer of high chemical purity. The central portion of the tapered block copolymer is rather a gradient composition of the two monomers.

In one embodiment, the poly(meth)acrylate polymer (P) comprises at least one polymer block (B ₁ ) that is insoluble or substantially insoluble in the base oil and a second polymer block (B 1 ) that is soluble or substantially soluble in the base oil. A block copolymer or tapered block copolymer comprising a polymer block (B ₂ ).

In one embodiment, the poly(meth)acrylate polymer can have a structure selected from linear, branched, hyperbranched, crosslinked, star (also referred to as "radial"), or combinations thereof. Star or radial refers to multi-arm polymers. Such polymers include (meth)acrylate-containing polymers comprising 3 or more arms or branches, and in some embodiments at least about 20, or at least 50, or 100 arms or branches; or 200, or 350, or 500, or 1000 carbon atoms. The arms are generally attached to a multivalent organic moiety that functions as a "core" or "coupling agent." Multi-armed polymers may be referred to as radial or star polymers, or even "comb" polymers, as otherwise described herein, as polymers having multiple arms or branches.

Random, block or other linear poly(meth)acrylates can have a weight average molecular weight (M _w ) of 1000-400,000 Daltons, 1000-150,000 Daltons, or 15,000-100,000 Daltons. . In one embodiment, the poly(meth)acrylate may be a linear block copolymer with Mw from 5,000 to 40,000 Daltons or from 10,000 to 30,000 Daltons.

Radial, crosslinked or star copolymers can be derived from linear random or diblock copolymers having the above molecular weights. Star polymers can have a weight average molecular weight of 10,000 to 1,500,000 daltons, or 40,000 to 1,000,000 daltons, or 300,000 to 850,000 daltons.

The lubricating composition comprises from 0.05 wt% to 2 wt%, or from 0.08 wt% to 1.8 wt%, or from 0.1 to 1.2 wt% of one or more polymers described herein It may contain a viscosity modifier.

In one embodiment, the present invention provides a lubricating composition further comprising a friction modifier. Examples of friction modifiers include long chain fatty acid derivatives of amines, fatty esters, or epoxides, fatty imidazolines such as condensation products of carboxylic acids and polyalkylene-polyamines, amine salts of alkylphosphoric acids, fatty alkyltartarates, Fatty alkyl tartrimides or fatty alkyl tartramides may be mentioned. As used herein, the term fatty may mean having a C8-22 straight chain alkyl group.

Friction modifiers may also include materials such as sulfurized fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil, or monoesters of polyols with aliphatic carboxylic acids.

In one embodiment, the friction modifiers include long chain fatty acid derivatives of amines, long chain fatty esters, or long chain fatty epoxides, fatty imidazolines, amine salts of alkyl phosphoric acids, fatty alkyl tartrates, fatty alkyl tartrimides, and. It may be selected from the group consisting of fatty alkyl tartramides. Friction modifiers may be present at 0% to 6%, or 0.05% to 4%, or 0.1% to 2%, by weight of the lubricating composition.

In one embodiment, the friction modifier may be a long chain fatty acid ester. In another embodiment, the long chain fatty acid ester may be a monoester or diester, or mixtures thereof, and in another embodiment the long chain fatty acid ester may be a triglyceride.

Other performance enhancing additives such as corrosion inhibitors include those described in paragraphs 5-8 of US Application No. 05/038319, published as WO 2006/047486, octyl octanamide, dodecenyl succinic acid or its anhydrides and condensation products of fatty acids such as oleic acid with polyamines. In one embodiment, the corrosion inhibitors include Synalox® (trademark of The Dow Chemical Company) corrosion inhibitors. Synalox corrosion inhibitors may be homopolymers or copolymers of propylene oxide. Synalox corrosion inhibitors are available on Form No. 1, published by The Dow Chemical Company. 118-01453-0702 AMS product brochure. The title of the product brochure is "SYNALOX Lubricants, High-Performance Polyglycols for Demanding Applications."

The lubricating composition further comprises a derivative of benzotriazole (typically tolyltriazole), a dimercaptothiadiazole derivative, a 1,2,4-triazole, a benzimidazole, a 2-alkyldithiobenzimidazole, or a 2-alkyldithiobenzo metal deactivators including thiazoles, suds suppressors including copolymers of ethyl acrylate and 2-ethylhexyl acrylate, copolymers of ethyl acrylate, 2-ethylhexyl acrylate and vinyl acetate, trialkyl phosphates, polyethylene glycol, polyethylene oxide, Demulsifiers including polypropylene oxide and (ethylene oxide-propylene oxide) polymers, and pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides may be included.

Pour point depressants that may be useful in the compositions of the present invention further include polyalphaolefins, esters of maleic anhydride-styrene, poly(meth)acrylates, polyacrylates, or polyacrylamides.

In different embodiments, the lubricating composition can have a composition as described in the table below.

The present invention provides a surprising ability to provide engine durability (ie, wear resistance) and increased fuel economy without increasing oil consumption.

Industrial Applications As noted above, the present invention provides a method for lubricating an internal combustion engine comprising supplying the internal combustion engine with the lubricating composition disclosed herein. Generally, lubricants are added to the lubrication system of an internal combustion engine to then deliver the lubricating composition to the critical parts of the engine that require lubrication during operation. Furthermore, the present disclosure relates to the use of the described lubricant composition in internal combustion engines to improve their fuel economy.

The lubricating composition described above can be utilized in internal combustion engines. Engine parts may have steel or aluminum surfaces (usually steel surfaces) and may be coated with, for example, a diamond-like carbon (DLC) coating.

Internal combustion engines may be fitted with emission control systems or turbochargers. Examples of emission control systems include systems using diesel particulate filters (DPF), gasoline particulate filters (GPF), three-way catalysts, or selective catalytic reduction (SCR).

Internal combustion engines can be spark ignited or compression ignited and will utilize fuels suitable for the ignition sequence. Spark ignited internal combustion engines can be port fuel injected (PFI) or direct injected.

Internal combustion engines can typically be fueled by liquid or gaseous fuels, or a combination thereof. Liquid fuels are typically liquid at ambient conditions such as room temperature (20-30° C.). The fuel can be hydrocarbon fuels, non-hydrocarbon fuels, or mixtures thereof. The hydrocarbon fuel may be gasoline as defined by ASTM specification D4814. In one embodiment of the invention the fuel is gasoline, in another embodiment the fuel is leaded or unleaded gasoline.

The internal combustion engine may operate at a brake mean effective pressure (BMEP) of at least 12 bar, or at least 20 bar, or at least 22 bar, or at least 24 bar, or at least 26 bar. In one embodiment, high BMEP comprises one or more features including gasoline direct injection (GDI), turbocharger, supercharger, variable valve timing, homogenous charge compression ignition (HCCI), lean burn, or combinations thereof. It is realized through running the engine.

Non-hydrocarbon fuels can be oxygen-containing compositions, often referred to as oxygenates, including alcohols, ethers, ketones, esters of carboxylic acids, nitroalkanes, or mixtures thereof. Non-hydrocarbon fuels can include, for example, transesterified oils and/or fats from plants and animals such as methanol, ethanol, methyl t-butyl ether, methyl ethyl ketone, rapeseed methyl ester and soybean methyl ester, or nitromethane. Mixtures of hydrocarbon and non-hydrocarbon fuels may include, for example, gasoline and methanol and/or ethanol. In one embodiment of the invention, the liquid fuel is a mixture of gasoline and ethanol, wherein the ethanol content is at least 5 volume percent of the fuel composition, or at least 10 volume percent of the composition, or at least 15 volume percent of the composition; or 15 to 85 volume percent of the composition. In one embodiment, the liquid fuel contains less than 15 vol.% ethanol content, less than 10 vol.% ethanol content, less than 5 vol.% ethanol content, or is substantially free of ethanol (i.e. , less than 0.5% by volume).

Gas fuels are typically gases at ambient conditions such as room temperature (20-30° C.). Suitable gas fuels include natural gas, liquefied petroleum gas (LPG), compressed natural gas, or mixtures thereof. In one embodiment, the engine is fueled with natural gas.

The lubricant composition has a maximum of about 32.5 cSt at 100°C, or from about 4.5 to about 18.5 cSt at 100°C, or from about 5.3 to about 13.5 cSt at 100°C, as measured by ASTM D445. , or an engine oil having a kinematic viscosity at 100° C. of from about 6 to about 10.5 cSt.

High temperature high shear (HTHS) is a viscosity measurement that represents the resistance to fluid flow under conditions similar to a highly loaded journal bearing in an internal combustion engine. The HTHS value of an oil and/or lubricating composition directly correlates to the thickness of the oil film in the bearing. HTHS values for fluids can be obtained by using ASTM D4683 at 150 degrees. C. Lubricating compositions of the present invention may have a HTHS from 1.8 cP to 3.2 cP, or from 2.3 cP to 2.6 cP, or less than 2.3 cP.

In one embodiment, the lubricating composition may be an engine oil, wherein the lubricating composition comprises (i) a sulfur content of 0.5 wt% or less; (ii) a phosphorus content of 0.1 wt% or less; (iii) having at least one of a sulfated ash content of 1.5% by weight or less, or a combination thereof;

The invention is further illustrated by the following examples, which set forth particularly advantageous embodiments. Examples are provided to illustrate the invention and are not intended to limit the invention.

Lubricating Base Oils A range of fluids are evaluated as base fluids for formulating lubricants suitable for internal combustion engines. Materials include conventional mineral oils, polyalphaolefins, and bioengineered hydrocarbon oils, as set forth in Table 1 below.

Lubricating Compositions A series of 0W-16 engine lubricants comprise the above base fluids along with ashless succinimide dispersants, overbased detergents, antioxidants (combinations of phenolic esters, diarylamines, sulfurized olefins), dialkyldithiolines. It is prepared containing conventional additives such as zinc acid (ZDDP), polymeric viscosity modifiers, as well as other performance additives. All lubricants are prepared based on a general formulation as shown in Table 2 below.

Testing Lubricants are evaluated for wear performance, fuel economy, friction reduction performance, and oil consumption. Many industry standard engine tests are used to evaluate engine lubricant performance and often have oil consumption measurements. Engine tests include the BMW N20 endurance engine oil test. The N20 test is a 395 hour test used to evaluate lubricating composition for piston cleanliness, engine sludge, turbocharger deposits, and wear iron; New European Drive Cycle (NEDC); API Sequence IIIH for measuring oxide deposit control; API Sequence IVB for measuring engine durability; and approval of gasoline engines in addition to API SN and API CK-4 diesel Many other things as part of engine approval.

The lubricants are evaluated for wear performance in a programmed temperature high frequency reciprocating rig (HFRR) available from PCS Instruments. The HFRR conditions for the evaluation were a load of 200 g, duration of 75 minutes, stroke of 1000 micrometers, frequency of 20 Hertz, and temperature profile at 40° C. for 15 minutes, followed by a temperature of 160° C. at a rate of 2° C. per minute. continue to increase to The wear scar in micrometers and film formation as a percent of film thickness were then measured at lower wear scar values and higher film formation values, indicating improved wear performance.

The percent film thickness is based on the measurement of the potential between the top and bottom metal test plates in the HFRR. At 100% film thickness, a high potential exists over the entire length of the 1000 micrometer stroke, suggesting no metal-to-metal contact. Conversely, at 0% film thickness, there is no potential to suggest continuous metal-to-metal contact between the plates. For intermediate film thicknesses, there is a potential, suggesting that the top and bottom metal test plates have some degree of metal-to-metal contact, and other areas with no metal-to-metal contact.

The lubricating compositions are tested for deposition control in a panel coker heated to 325°C, a sump temperature of 105°C, and a splash/bake cycle of 120s/45s. The airflow is 350 ml/min, the spindle speed is 1000 rpm and the test lasts 4 hours. The oil is splashed onto an aluminum panel and then optically evaluated by a computer. The performance range is from 0% (black panel) to 100% (clean panel).

The propensity for lubricating compositions to resist deposit formation is evaluated with the Komatsu Hot Tube (KHT) test. This was done by circulating a sample of engine oil at 0.31 mL per hour and 10 mL per minute of air through a glass tube at a specified temperature, typically 270° C. up to 310° C., for 16 hours. An industry test used to evaluate the performance of engine oils based on their deposit forming tendencies. After testing, the tubes were rated visually, with higher numbers being better ratings: 10 representing a clean tube and 0 (zero) representing a deposit-rich tube.

Deposit performance can be measured according to the Thermal Oxidation Engine Oil Simulation Test (TEOST 33), as set forth in ASTM D6335. The TEOST 33 test results represent milligrams of deposits after running the engine oil at elevated temperatures. Lower TEOST 33 results indicate improved resistance to deposit formation.

Some of the above substances are known to interact in the final formulation, so the components of the final formulation may differ from those initially added. Products formed according to this specification, including those formed upon using the lubricant composition of the present invention in its intended use, may not be easily described. Nonetheless, all such modifications and reaction products are included within the scope of this invention, which includes lubricant compositions prepared by admixing the above components.

Each of the above-referenced documents, if any priority documents and all related applications to which this application claims the benefit, is hereby incorporated by reference herein, in the Examples or otherwise expressly indicated. Except where indicated, all numbers in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, etc. should be understood to be modified by the word "about." Unless otherwise specified, each chemical or composition referred to herein is a commercial grade material that may contain isomers, by-products, derivatives, and other such materials commonly understood to be present in commercial grades. should be interpreted as However, unless otherwise indicated, the amount of each chemical component is presented exclusive of any solvents and diluents that may be customarily present in commercially available materials. It is to be understood that the upper and lower limits of amounts, ranges, and ratios set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the invention may be used together with ranges or amounts for any of the other elements.

As used herein, the terms "hydrocarbyl substituent" or "hydrocarbyl group" are used in their ordinary sense and are well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include hydrocarbon substituents, i.e. aliphatic substituents (e.g. alkyl or alkenyl), alicyclic substituents (e.g. cycloalkyl, cycloalkenyl), and aromatic substituted aromatic substituents. , aliphatic-substituted aromatic substituents, and alicyclic-substituted aromatic substituents, and cyclic groups in which the ring is completed through another part of the molecule (e.g., two substituents together form a ring) Substituents, (ii) substituted hydrocarbon substituents, i.e., in the context of this invention, substituents containing non-hydrocarbon groups that do not alter the predominantly hydrocarbon character of the substituent, such as halo (particularly chloro and fluoro ), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso and sulfoxy); Hetero substituents containing or otherwise composed of carbon atoms are included.

Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents such as pyridyl, furyl, thienyl, and imidazolyl. Generally, no more than 2, preferably no more than 1, non-hydrocarbon substituents will be present for every 10 carbon atoms in the hydrocarbyl group, and there will normally be no non-hydrocarbon substituents on the hydrocarbyl group.

As used herein, the singular forms “a,” “an,” and “the” include plural references unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Nothing in this disclosure is to be construed as an admission that the embodiments described in this disclosure are not entitled to antedate such disclosure by virtue of prior invention. As used herein, the term "including" means "including but not limited to."

Various compositions, methods, and apparatus are described by the word "comprising" various components or steps (which is to be construed to mean "including but not limited to"). but the compositions, methods, and apparatus may also “consist essentially of” or “consist of” the various components and steps thereof, and such terms are essentially closed. should be interpreted as defining a group of elements that

Various compositions, methods, and devices are described by the term "comprising" various components or steps (which is interpreted to mean "including, but not limited to," ), the compositions, methods, and apparatus may also be “consisting essentially of” or “consisting of” the various components and steps thereof, and such terms are essentially closed It should be interpreted as defining a group of elements.

It will be understood by those skilled in the art that the terms used generally in this specification, and particularly in the appended claims (e.g., the body of the appended claims), are generally intended as "open" terms ( For example, the term "including" should be construed as "including but not limited to" and the term "having" should be construed as "having at least" and "including" should be interpreted as "including, but not limited to"). It will be appreciated by those skilled in the art that where any particular number of introduced claim recitations is intended, such intentions are expressly set forth in the claims, and that such intentions do not exist in the absence of such recitations. will understand more. For example, as an aid to understanding, the claims appended hereto may contain usage of the introductory phrases "at least one" and "one or more" to introduce claim recitations. However, use of such phrases means that a claim recitation introduced with the indefinite article "a" or "an" may exclude any particular claim containing such recitation from such recitation. is not to be interpreted as being meant to be limited to embodiments containing only one of, and the same claim may include the introductory phrases "one or more" or "at least one" and "a" or "an", etc. (e.g., "a" and/or "an" should be construed to mean "at least one" or "one or more") is). The same holds true for the use of definite articles used to introduce claim recitations. Further, even where a particular number of the introduced claim recitations is explicitly recited, one skilled in the art will recognize that such recitation means at least the number recited (e.g., with other modifiers). It will be appreciated that a reference to only "two references" without a reference is to be construed as meaning at least two references, or more than two references. Further, where similar phrases are used, such as "at least one of A, B, and C," such constructs are generally intended in the sense of that phrase as understood by those skilled in the art. (e.g., "a system having at least one of A, B, and C" refers to a system having only A, a system having only B, a system having only C, a system having both A and B, A and C together, a system having both B and C, and/or a system having both A and B and C, etc.). Where a phrase similar to "at least one of A, B, or C" is used, such constructs are generally intended in the sense of that phrase as the skilled person will understand ( For example, "a system having at least one of A, B, or C" means a system having only A, a system having only B, a system having only C, a system having both A and B, A and C , B and C together, and/or A and B and C together, etc.). Substantially any disjunctive word and/or phrase presenting two or more alternative items, whether in the specification, claims, or drawings, , may include one of those items, may include either of those items, or may include both of those items. would be For example, the phrase "A or B" is understood to include the possibilities of "A" or "B" or "A and B."

Furthermore, where a feature or aspect of the disclosure can be described in terms of a Markush group, those skilled in the art will appreciate that the disclosure can also be described in terms of any individual element or subgroup of elements of the Markush group. Will.

As will be appreciated by those of skill in the art, all ranges disclosed herein also include any and all possible sub- Combinations of ranges and subranges thereof are included. any recited range fully describes dividing that same range into at least equal halves, into thirds, quarters, fifths, tenths, etc.; and can be easily recognized as enabling this. As a non-limiting example, each range discussed herein can be readily divided into a bottom third, a middle third, a top third, and so on. Also, as will be appreciated by those of ordinary skill in the art, all language such as "until", "at least", etc. includes the stated number and ranges that can later be divided into subranges as discussed above. point to Finally, as understood by one of ordinary skill in the art, ranges are inclusive of each individual element. Thus, for example, a group having 1-3 weight percent refers to groups having 1, 2, or 3 weight percent. Similarly, a group having 1 to 5 weight percent refers to groups having 1, 2, 3, 4, or 5 weight percent, etc., including all points therebetween.

As used herein, the term "about" means that the value of a given quantity is within ±20% of the indicated value. In other embodiments, the values are within ±15% of the indicated value. In other embodiments, the values are within ±10% of the indicated value. In other embodiments, the values are within ±5% of the indicated value. In other embodiments, the value is within ±2.5% of the stated value. In other embodiments, the values are within ±1% of the indicated value.

Unless otherwise specified, "wt%" as used herein shall refer to weight percent (weight percent) based on the total weight of the lubricating composition.

Although the invention has been described in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. It is therefore to be understood that the invention disclosed herein is intended to cover such modifications as come within the scope of the appended claims.

Claims (39)

A low viscosity, low volatility lubricating composition comprising
An oil of lubricating viscosity comprising a lubricating base oil and a hydrocarbon oil, said hydrocarbon oil being at least 20% by weight of said oil of lubricating viscosity, a kinematic viscosity at 100° C. of less than 3.7 cSt, and 25 wt. an oil of lubricating viscosity having a NOACK volatility (as measured by ASTM D5800) of less than
1.2-4% by weight of a polyalkenylsuccinimide dispersant;
A low viscosity, low volatility lubricating composition wherein said lubricating composition is a 0W-XX multigrade composition according to SAE J300, and XX is selected from 8, 12, 16, and 20. 2. The composition of claim 1, wherein said oil of lubricating viscosity has a viscosity index greater than 100. 3. The composition of claim 1 or 2, wherein said oil of lubricating viscosity has a viscosity index greater than 110. A composition according to any one of the preceding claims, wherein said oil of lubricating viscosity has a viscosity index greater than 115. A composition according to any one of the preceding claims, wherein the oil of lubricating viscosity has a viscosity index of greater than 125. A composition according to any one of the preceding claims, wherein said oil of lubricating viscosity has a viscosity index of 110-130. A composition according to any one of the preceding claims, wherein said oil of lubricating viscosity has a viscosity index of 115-125. A composition according to any one of the preceding claims, wherein said oil of lubricating viscosity has a viscosity index of 117-122. A composition according to any one of the preceding claims, wherein at least 50% by weight of said hydrocarbon oil is of biological origin. A composition according to any one of the preceding claims, wherein the hydrocarbon oil is of biological origin and substantially free of ester functional groups. 11. The composition of claim 10, wherein said biologically derived hydrocarbon oil comprises hydrocarbon compounds having a continuous chain of no more than 24 carbon atoms and a total of at least 30 carbon atoms. A composition according to any one of the preceding claims, wherein the lubricating composition has no more than 10 wt% polyalphaolefin base oil. A composition according to any one of the preceding claims, wherein said oil of lubricating viscosity has at least 40% by weight of said hydrocarbon oil. A composition according to any one of the preceding claims, wherein said oil of lubricating viscosity has at least 50% by weight of said hydrocarbon oil. A composition according to any one of the preceding claims, wherein said oil of lubricating viscosity has at least 60% by weight of said hydrocarbon oil. A composition according to any one of the preceding claims, wherein the hydrocarbon oil has a kinematic viscosity at 100°C of less than 3.6 cSt. A composition according to any one of the preceding claims, wherein the hydrocarbon oil has a kinematic viscosity of 3.5 cSt at 100°C or less. A composition according to any one of the preceding claims, wherein the hydrocarbon oil has a kinematic viscosity at 100°C of less than 3.4 cSt. A composition according to any one of the preceding claims, wherein the hydrocarbon oil has a NOACK volatility of less than 20 wt%. A composition according to any one of the preceding claims, wherein the hydrocarbon oil has a NOACK volatility of less than 15 wt%. A composition according to any one of the preceding claims, wherein the hydrocarbon oil comprises branched hydrocarbon compounds containing at least 16 carbon atoms and no more than 60 carbon atoms. A composition according to any one of the preceding claims, wherein said hydrocarbon oil comprises from 20% to 95% by weight of said oil of lubricating viscosity. A composition according to any one of the preceding claims, further comprising a polymeric viscosity modifier. 22. The composition of claim 21, wherein said polymeric viscosity modifier is present in said lubricating composition in an amount of 0.05 to 2% by weight. 22. The composition of claim 21, wherein said polymeric viscosity modifier is present in said lubricating composition in an amount of 0.08 to 1.8 weight percent. 22. The composition of claim 21, wherein said polymeric viscosity modifier is present in said lubricating composition in an amount of 0.1 to 1.2 weight percent. A composition according to any one of the preceding claims, wherein the hydrocarbon oil is substantially aliphatic and contains less than 5% by weight of cyclic hydrocarbons. A composition according to any one of the preceding claims, wherein the polyalkenylsuccinimide dispersant is polyisobutylene succinimide. A composition according to any one of the preceding claims, wherein the polyalkenyl dispersant is present in the lubricating composition in an amount of 1.2-3% by weight. A composition according to any one of the preceding claims, wherein the polyalkenyl dispersant comprises a boron-containing succinimide in an amount of 0.5-4% by weight of the lubricating composition. A composition according to any one of the preceding claims, further comprising an antiwear agent. 29. The composition of claim 28, wherein said antiwear agent is present in said lubricating composition in an amount of 0.1-3% by weight. 31. The composition of claim 29 or 30, wherein the antiwear agent is a zinc dialkyldithiophosphate. A composition according to any one of the preceding claims, further comprising a metal-containing detergent. 35. The composition of claim 34, wherein the metal-containing detergent is present in the lubricating composition in an amount of 0.5-3% by weight. 36. The composition of claims 34 or 35, wherein the metal-containing detergent comprises one or more of an overbased calcium detergent, an overbased magnesium detergent, and combinations thereof. 37. The composition of any one of claims 34-36, wherein the metal-containing detergent comprises a detergent selected from one or more of a calcium salicylate detergent, a magnesium salicylate detergent, and combinations thereof. thing. A method of lubricating an internal combustion engine, comprising:
A method comprising supplying a lubricating composition according to any one of the preceding claims to the internal combustion engine. Use of a lubricating composition according to any one of claims 1 to 37 for improving the fuel economy of internal combustion engines.